Reactions with isopentane in the presence of a liquid catalyst



Patente ci Aug. 20,1946

" UNITED STATES REACTIONS WITH ISOPENTANE IN THE M PRESENCE OFA LIQUID CATALYST Robert E. Burk, Cleveland Heights, Ohio, assign or to The Standard Oil Company, Cleveland, I 7

Ohio, a corporation of Ohio No Drawing. Application July 16, 1942,

' Serial No. 451,216

This invention relates to a process of averaging hydrocarbons; in which one of the react-v ably isobutan'e, with hydrocarbons of higher molecular weight. I'have found that when isopentan'e is applied in reaction with hydrocarbons of six or more carbon atoms, large quantities of isobutane are formed along with highly branched gasoline fractions. 'Neohexane, in particular, is readily made by thus averaging with isopentane.

And, generally isopentane or mixtures of isopen-' tane and normally gaseous hydrocarbons maybe reacted'with hydrocarbons of more than five carbon' atoms such that products in the gasoline range are obtained.

To the accomplishment of the foregoing and related ends, the invention, 'then, comprises the features hereinafter fully described, and particularly pointed out in the claims, the following descriptio'nsetting forth in detail" certain illustra: tive embodiments of-the-invention, these being indicative however,'of but a-few' ofz'the'various ways in which the principle of the-invention'may be employed. f

Any convenient source ofhydrocarbons may be used, and isopentane or mixtures thereof with lower hydrocarbons ar ap-plicable for-the lightor component, the isopentane or' mixtures being 'used'in amounts of 1 10 mols per mol of heavier hydrocarbon; The heavier hydrocarbons employed are those containing preferably more than six carbon atoms. Where hydrocarbon stocks contain aromatic compounds these may be first removed by extracting with selective solvents or by reacting out in formation of complexes with the catalyst, although reaction can be proceeded within spite of th aromatic content. Desirably, the aromatic content should be less than 2 per cent. The material may contain other unsaturated hydrocarbons. Kerosene and gas oildistillates are preferred stocks.

. The catalyst consists of liquid hydrofluoric acid in which one-half to 50 mol per cent of boron fluoride is dissolved. The partial pressure of boron fluoride may be 5-550 pounds per square inch, and preferably 150 pounds. The amount recl ims. (01. 196-78) ofsuch promoted catalyst applied. to the hydrocarbon may bet-300 volume per cent ofthe liqv uid hydrocarbon used. The amount of boron flu-- oride applied depends upon the desired activityof the catalyst. Very exact control of the catalyst and a particularly flexible control of operation and product is thus possible. The-pressure is maintained sufficient to keep the hydrogen flu- D oride in liquid state. The catalyst may finallybe separated from the hydrocarbons and be returned for reaction with the incoming feed.

The temperatures may be relatively low, minus 1 30 C. up, and particularly 20 to C. In reaction with isopentane and hydrocarbons of at least six carbon atoms, the course of the reaction may be'represented as follows:

Isopentane+CnHz1 ++i butane+branched hexanes, heptanes, wanes; etc. j I

As an example:- A kerosene distillate from" 1111- nois petroleum was reacted'with 4.9 mols of i-peh tane per mol of kerosene at 32C., the catalyst being 33 volume per cent HF used with pounds partial pressure of BFs, and reaction time two hours. The product showed 77.6 percent of the total charge that was converted, the products comprising 0.75 per cent ofpropane, 42.8 per cent of isobutane, 16.2 per cent of neohexane, and a gasoline yield of 37 per cent.

As another example: A similar kerosene distillate was reacted with a mixture of isopentane and a butane fraction containing 15 per centof isopentane at 0 C.,- the mol ratios of the hydrocarbon for reaction being 5.3 0411.45 C521 .keroe. sene. The catalyst was 28.3 volume per cent of HF used with 150 pounds pressure of BFs. The product showed 96.6 per cent of the total charge converted. Of the product, 86.3 weight 'per cent was a gasoline, including 2,3 dimethylbutane and triptane as shown by the Ewell distillation curve.

By averaging as used herein I mean the reaction of a higher and a lower molecular weight hydrocarbon to form a hydrocarbon of intermediate molecular weight.

Other modes of applying the principle of the invention may be employed, chang being made as regards the details described, provided the features stated in any of the following claims, or the equivalent of such, be employed.

1 therefore particularly point out and distinctly claim as my invention:

1. A process of averaging a liquid petroleum fraction comprised primarily of normal hydrocarbons having at least six carbon atoms, with another petroleum fraction containing an appreciable amount of isopentane, in th presence of a catalyst comprised essentially of liquid hydrogen fluoride in which is dissolved not over 50 mol percent of boron trifiuoride (based on the hydrogen fluoride) to provide a partial pressure of boron trifiuoride of 5 to 550 pounds per square inch and continuing the reaction under a pressure to maintain the hydrogen fluoride liquid thereby to form hydrocarbons intermediate said reacting petroleum fractions.

2. A process of averaging a liquid petroleum fraction comprised primarily of normal hydrocarbons having at least six carbon atoms, with another petroleum fraction containing butane and an appreciable amount of isopentane, in the presence of a catalyst comprised essentially of liquid hydrogen fluoride in which is dissolved not over mol percent of boron trifluoride (based on the hydrogen fluoride) to provide a partial pressure of boron trifluoride of 5 to 550 pounds per square inch, and continuing the reaction under a pressure to maintain the hydrogen fluoride liquid thereby to form hydrocarbons intermediate said reacting petroleum fractions.

3. A process of averaging a liquid petroleum fraction comprised primarily of normal hydrocarbons having at least six carbon atoms and boiling in the gas oil-kerosene range, with another petroleum fraction containing an appreciable amount of isopentane, at a temperature of not over 100 C, and in the presence of 5 to 300 volume percent (based on the liquid hydrocarbons) of a catalyst comprised essentially of liquid hydrogen fluoride in which is dissolved not over 50 mol percent of boron trifiuoride (based on the hydrogen fluoride) to provide a partial pressure of boron trifluoride of 5 to 550 pounds per square inch, and continuing the reaction under a pressure to maintain the hydrogen fluoride liquid thereby to form hydrocarbons intermediate said reacting petroleum fractions.

4. A process of averaging a liquid petroleum fraction comprised primarily of normal hydrocarbons having at least siX carbon atoms and boiling in the gas oil-kerosene range, with another petroleum fraction containing butane and an appreciable amount of isopentane, at a temperature of not over 100 C., and in the presence of 5 to 300 volume percent (based on the liquid hydrocarbons) of a catalyst comprised essentially of liquid hydrogen fluoride in Which is dissolved not Over 50 mol percent of boron trifluoride (based on the hydrogen fluoride) to provide a partial pressure of boron trifluoride of 5 to 550 pounds per square inch, and continuing the reaction under a pressure to maintain the hydrogen fluoride liquid thereby to form hydrocarbons intermediate'said reacting petroleum fractions.

5. A process of averaging kerosene with another petroleum fraction containing an appreciable amount of isopentane, at a temperature of not over 100 C. and in the presence of 5 to 300 volume percent (based on the liquid hydrocarbons) of a catalyst comprised essentially of liquid hydrogen fluoride in which is dissolved not over 50 mol percent of boron trifiuoride (based on the hydrogen fluoride) toprovide a partial pressure of boron trifluoride of 5 to 550 pounds per square inch, and continuing the reaction under .a pressure to maintain the hydrogen fluoride liquid thereby to form hydrocarbons intermediate said kerosene and said isopentane.:

6. A process of averaging kerosene with another petroleum fraction containing butane and an appreciable amount of isopentane, at a tem- 4 perature of not over C. and in the presence of 5 to 300 volume percent (based on the liquid hydrocarbons) of a catalyst comprised essentially of liquid hydrogen fluoride in which is dissolved not over 50 mol percent of boron trifluoride (based on the hydrogen fluoride) to provide a partial pressure of boron trifiuoride of 5 to 550 pounds per square inch, and continuing the reaction under a pressure to maintain the hydrogen fluoride liquid thereby to form hydrocarbons intermediate said kerosene and said isopentane.

7. A process of averaging gas oil with another petroleum fraction containing an appreciable amount of isopentane, at a temperature of not over 100 C. and in the presence of 5 to 300 volume percent (based on the liquid hydrocarbons) of a catalyst comprised essentially of liquid hydrogen fluoride in which is dissolved not over 50 mol percent of boron trifluoride (based on the hydrogen fluoride) to provide a partial pressure of boron trifluoride of 5 to 550 pounds per square inch, and continuing the reaction under a pressure to maintain the hydrogen fluoride liquid thereby to. form hydrocarbons intermediate said gas oil and said isopentane.

8. A process of averaging a liquid petroleum fraction comprised primarily of normal hydrocarbons having at least six carbon atoms and boiling in the gas oil-kerosene range, with another petroleum fraction containing an appreciable amount of isopentane, at a temperature of not over 100 C. and in the presence of 5 to 300 volume percent (based on the liquid hydrocarbons) of a catalyst the catalytic ingredients of which are comprised essentially of liquid hydrogen fluoride in which is dissolved not over 50 mol percent of boron trifluoride (based on the hydrogen fluo-,

ride) to provide a partial pressure of boron trifluoride of 5 to 550 pounds per square inch, the activity of said catalyst being controllable by the regulation of the partial pressure of the boron trifiuoride, and continuing the reaction under a pressure to maintain the hydrogen fluoride liquid, whereby substantial amounts of isobutane and branched chain hydrocarbons intermediate said reacting petroleum fractions are formed. 1

9. A process of averaging a liquid petroleum fraction comprised primarily of normal hydrocarbons having at least six carbon atoms and boiling in the gas oil-kerosene range, with another petroleum fraction containing butane and an appreciable amount of isopentane, at a, temperature of not over 100 C. and in the presence of 5 to 300 volume percent (based on the liquid hydrocarbons) of a catalyst the catalytic ingredients of which are comprised essentially of liquid hydrogen fluoride in which is dissolved not over 50 mol percent of boron trifiuoride (based on the hydrogen fluoride) to provide a partial pressure of boron trifiuoride of 5 to 550 pounds per square inch, the activity of said catalyst being controllable by the regulation of the partial pressure of the boron trifiuoride, and continuing the reaction under a pressure to maintain the hydrogen fluoride liquid, whereby substantial amounts of isobutane and branched chain hydrocarbons in the gasoline range are formed.

10. 'A process of averaging a kerosene fraction with at least one mol of isopentane per mol .of kerosene, at a temperature of not over 100 C. and in the presence of 5 to 300 volume percent (based on the liquid hydrocarbons) of .a catalyst the catalytic ingredients of which are comprised essentially vof liquid hydrogen fluoride in which is dissolved not over 50 mol percent of boron trifiuoride (based on the hydrogen fluoride) to provide a partial pressure of boron trifiuoride of 5 to 550 pounds per square inch, the of said catalyst being controllable by the regulation of the partial pressure of the boron trifluoride, and continuing the reaction under a pressure to maintain the hydrogen fluoride liquid, whereby substantial amounts of isobutane and branched chain hydrocarbons in the gasoline range are formed.

11. A process of averaging kerosene with at least one mol of isopentane per mol of kerosene and in the presence of butane, at a temperature of not over 100 C. and in the presence of 5 to 300 volume percent (based on the liquid hydrocarbons) of a catalyst the catalytic ingredients of which are comprised essentially of liquid hydrogen fluoride in which is dissolved not over 50 mol percent of boron trifiuoride (based on the hydrogen fluoride) to provide a partial pressure of boron trifiuoride of 5 to 550 pounds per square inch, the activity of said catalyst being controllable by the regulation of the partial pressure of the boron trifiuoride, and continuing the activity reaction under a pressure to maintain the hydrogen fluoride liquid, whereby substantial amounts of isobutane and branched chain hydrocarbons in the gasoline range are formed.

12. A process of averaging a gas oil fraction with at least one mol of isopentane per mol of gas oil, at a temperature of not over 100 C. and in the presence of 5 to 300 volume percent (based on the liquid hydrocarbons) of a catalyst the catalytic ingredients of which are comprised essentially of liquid hydrogen fluoride in which is dissolved not over 50 mol percent of boron trifiuoride (based on the hydrogen fluoride) to provide a partial pressure of boron trifiuoride of 5 to 550 pounds per square inch, the activity of said catalyst being controllable by the regulation of the partial pressure of the boron trifiuoride, and continuing the reaction under a pressure to maintain the hydrogen fluoride liquid, whereby substantial amounts of isobutane and branched chain hydrocarbons in the gasoline range are formed.

ROBERT E. 'BURK. 

